The mechanism of the proton_transfer_coupled electron transfer (PT_ET) reactions between the menaquinone Q A (MQ 1) and ubiquinone Q B (UQ 1) in the bacterial photosynthetic reaction center of Rhodopseudomona vi...The mechanism of the proton_transfer_coupled electron transfer (PT_ET) reactions between the menaquinone Q A (MQ 1) and ubiquinone Q B (UQ 1) in the bacterial photosynthetic reaction center of Rhodopseudomona viridis was studied by using the B3LYP/6_31G(d) method. The changes of standard Gibbs free energy ΔG 0 of all possible reactions followed the ET reaction (1) were calculated. The results indicated that: (1) according to the ΔG 0 values of corresponding reactions, UQ 1 could not accept two electrons from MQ - 1 continually without the coupled proton transfer reactions. Because of ΔG 0 2b 0, ΔG 0 3b 0 and ΔG 0 4b 0, the corresponding PT_ET reactions could take place along with reactions (2b), (3b) and (4b) sequentially; (2) on the gaseous condition, the first and second transferred protons (H +(1) and H +(2)) from the surrounding amino acid residues or water molecules will combine with the oxygen No.7 and oxygen No.8 of UQ 1, respectively. On the condition of protein surroundings (by SCRF model, ε =4.0), the results are converse but the energy difference between the combination of H +(1) and H +(2) with UQ - 1 is quite small. The difference of ΔG 0 values between the corresponding reactions in gaseous surroundings and the SCRF model is not significant; (3) the PT_ET reactions between MQ 1 - and UQ 1 - should be as follows: MQ 1 -+UQ 1→MQ 1+UQ 1 - (1) UQ 1 - ( O (7) )+H +( HisL 190)→UQ 1H(2b) ( Gas ) or UQ 1 - ( O (8) )+H +(H 2O)→UQ 1H (2b') ( SCRF ) or UQ 1 - ( O (8) )+H + ( ArgL 217)→UQ 1H(2b') ( SCRF ) MQ 1 -+UQ 1H→MQ 1+UQ 1H - (3b) ( Gas ) MQ 1 -+UQ 1H→MQ 1+UQ 1H -(3b') ( SCR F) UQ 1H -+H +(H 2O)→UQ 1H 2(4b) ( Gas ) or UQ 1H -+H + ( ArgL 217)→UQ 1H 2 (4b) ( Gas ) or UQ 1H -+H + ( HisL 190)→UQ 1H 2 (4b') ( SCRF )展开更多
Acyl-ACP thioesterases (FATs) terminates the fatty acid synthesis and allow the transport of fatty acids out of the plastids, which are the important determinants of cellular metabolism. FATB is a member of FAT enzy...Acyl-ACP thioesterases (FATs) terminates the fatty acid synthesis and allow the transport of fatty acids out of the plastids, which are the important determinants of cellular metabolism. FATB is a member of FAT enzymes that has been described previously in most of the plants. In silico cloning is a new method that utilizes the bioinformatics on the complete genome and available EST database. In this study, a full-length cDNA clone of PtFATB gene was isolated from Populus tomentosa using this approach. It is 1,450 bp in length and the open reading frame encodes a peptide of 421 amino acids. The predicted amino acid sequence shows significant homology with those from other plant species, which contain typical domains owned by FATB proteins. The transcripts of PtFATB were abundant in leaves, and less in roots detected by using semiquantitative RT-PCR. When the shoots were subjected to the stress treatments (cold, dry, NaC1) and ABA (Abscisic acid), the expression of PtFATB was only slightly reduced under the treatment of low temperature. This suggests that the expression of PtFATB is in a constitutive fashion. This study provides the basis not only for the identification and characterization of this gene but also for the improvement of cold tolerance by controlling the expression of the PtFATB gene in trees in near future.展开更多
The reverse snapback phenomena (RSP) on I-V characteristics of static induction thyristors (SITH) are physically researched. The I-V curves of the power SITH exhibit reverse snapback phenomena, and even turn to th...The reverse snapback phenomena (RSP) on I-V characteristics of static induction thyristors (SITH) are physically researched. The I-V curves of the power SITH exhibit reverse snapback phenomena, and even turn to the conducting-state,when the anode voltage in the forward blocking-state is increased to a critical value. The RSP I-V characteristics of the power SITH are analyzed in terms of operating mechanism, double carrier injection effect, space charge effect, electron-hole plasma in the channel, and the variation in carrier lifetime. The reverse snapback mechanism is theoretically pro- posed and the mathematical expressions to calculate the voltage and current values at the snapback point are presented. The computing results are compared with the experiment values.展开更多
A series of donor-π-acceptor (D-π-A) compounds involving varied donors and acceptors as well as a dihydroquinolinone moiety were synthesized. Tuned fluorescent colors from blue to orange were successfully realized...A series of donor-π-acceptor (D-π-A) compounds involving varied donors and acceptors as well as a dihydroquinolinone moiety were synthesized. Tuned fluorescent colors from blue to orange were successfully realized in them. Spectroscopic analysis exhibits that the increased conjugated system, enhanced electrondonating ability of acceptor, and electron-withdrawing ability of donor result in red shift in both absorption and fluorescence for these compounds. Both the absorption and fluorescence show strong bathochromic shift effect with the increase in the polarity of solvents. It indicates that they are intramolecular charge transfer (ICT) fluorescent compounds and may have potential application as novel electroluminescent material.展开更多
A new anion receptor bearing phenolic hydroxy group based on 3,5- ditertbutylsalicylaldehyde-p-nitrophenylhydrazone (1) was designed and synthesized. Upon addition of AcO- and F-, the receptor exhibited visible colo...A new anion receptor bearing phenolic hydroxy group based on 3,5- ditertbutylsalicylaldehyde-p-nitrophenylhydrazone (1) was designed and synthesized. Upon addition of AcO- and F-, the receptor exhibited visible color changes from deep yellow to purple. However, no obvious color changes were observed on addition of the other anions tested (H2PO4-, Cl-, Br-, I-). The binding properties of the receptor with anions such as AcO and F- were investigated by UV-Vis and fluorescent titrations. The result indicated that the receptor 1 had a higher affinity to AcO- and F- and a 1:1 host-guest complex was formed through H-bond interactions between 1 and anions.展开更多
The excited state intramolecular proton transfer (ESIPT) coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the ...The excited state intramolecular proton transfer (ESIPT) coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the absorption peak from S1 excited state both in the experi-mental and calculated absorption spectra indicates that S1 is a dark state. The dark excited state S1 results in the very weak fluorescence of solid baicalein in the experiment. The fron- tier molecular orbital and the charge difference densities of baicalein show clearly that the S1 state is a charge-transfer state whereas the S2 state is a locally excited state. The only one stationary point on the potential energy profile of excited state suggests that the ESIPT reaction of baicalein is a barrierless process.展开更多
The divergent behavior of C-H bond oxidations of aliphatic substrates compared to those of aromatic substrates shown in Gupta’s experiment was mechanistically studied herein by means of density functional theory calc...The divergent behavior of C-H bond oxidations of aliphatic substrates compared to those of aromatic substrates shown in Gupta’s experiment was mechanistically studied herein by means of density functional theory calculations.Our calculations reveal that such difference is caused by different reaction mechanisms between two kinds of substrates(the aliphatic cyclohexane,2,3-dimethylbutane and the aromatic toluene,ethylbenzene and cumene).For the aliphatic substrates,C-H oxidation by the oxidant Fe^(V)(O)(TAML)is a hydrogen atom transfer process;whereas for the aromatic substrates,C-H oxidation is a proton-coupled electron transfer(PCET)process with a proton transfer character on the transition state,that is,a proton-coupled electron transfer process holding a proton transfer-like transition state(PCET(PT)).This difference is caused by the strongπ-πinteractions between the tetra-anionic TAML ring and the phenyl ring of the aromatic substrates,which has a“pull”effect to make the electron transfer from substrates to the Fe=O moiety inefficient.展开更多
Deuterium labeling techniques are widely utilized as efficient tools to study the absorption,distribution,metabolism,and excretion(ADME)of pharmaceuticals.Moreover,deuterium‐labeled drugs are expected to prolong the ...Deuterium labeling techniques are widely utilized as efficient tools to study the absorption,distribution,metabolism,and excretion(ADME)of pharmaceuticals.Moreover,deuterium‐labeled drugs are expected to prolong the half‐life of drug metabolism,enhance the efficacy of drugs,close metabolic sites,and decrease side effects.Thus,there is a rising demand for the practical construction of deuterium‐labeled drugs and their intermediates under mild conditions.This paper timely provides an overview of the recent advances in both photo‐and electro‐catalytic mild and selective deuteration of fine chemicals and pharmaceuticals with low‐cost and sustainable deuterium source.Three types of deuteration strategies are discussed according to the deuteration mode,named deuterium atom transfer strategy,deuterium atom abstraction strategy and deuterated water splitting strategy respectively.The application scope and mechanistic insights are discussed comprehensively.Finally,the perspective on the challenges and future development trends for photo‐and electro‐catalytic deuteration strategies are also presented.展开更多
Cyano substitution has been established as a viable approach to optimize the performance of all-small-molecule organic solar cells.However,the effect of cyano substitution on the dynamics of photo-charge generation re...Cyano substitution has been established as a viable approach to optimize the performance of all-small-molecule organic solar cells.However,the effect of cyano substitution on the dynamics of photo-charge generation remains largely unexplored.Here,we report an ultrafast spectroscopic study showing that electron transfer is markedly promoted by enhanced intermolecular charge-transfer interaction in all-small-molecule blends with cyanided donors.The delocalized excitations,arising from intermolecular interaction in the moiety of cyano-substituted donor,undergo ultrafast electron transfer with a lifetime of∼3 ps in the blend.In contrast,some locally excited states,surviving in the film of donor without cyano substitution,are not actively involved in the charge separation.These findings well explain the performance improvement of devices with cyanided donors,suggesting that manipulating intermolecular interaction is an efficient strategy for device optimization.展开更多
A new configuration integrated ion exchange effect with both electro-migration and electrochemical reaction in a single cell was developed to effectively retrieve metal ions from simulated wastewater using ion exchang...A new configuration integrated ion exchange effect with both electro-migration and electrochemical reaction in a single cell was developed to effectively retrieve metal ions from simulated wastewater using ion exchange resins without additive chemicals. By simply assembling cation exchange resins and anion exchange resins separated by homogeneous membranes, we found that the system will always be acidic in the concentrate compartment so that ion exchange resins could be in-situ regenerated without hydroxide precipitation. Such a realizable design will be really suitable for wastewater purification.展开更多
Photo-induced electron transfer versus molecular structure of acceptors is investigated using ultrafast time-resolved transient grating spectroscopy. Typical laser dyes Rhodamine 101 (Rh101) and Rhodamine 6G (Rh6G) in...Photo-induced electron transfer versus molecular structure of acceptors is investigated using ultrafast time-resolved transient grating spectroscopy. Typical laser dyes Rhodamine 101 (Rh101) and Rhodamine 6G (Rh6G) in electron donor solvent-aniline are adopted as the objects. The forward electron transfer time constant from aniline to the excited singlet state of two Rhodamine dyes and subsequent back electron transfer from two dyes to aniline are measured. The experimental results denote that Rh6G presents faster electron transfer rates with aniline in both forward electron transfer and back electron transfer processes. With chemical calculation and qualitative analysis, it is found that the flexible molecular geometry of Rh6G leads to stronger electron coupling with donor solvent and further gives rise to larger electron transfer rates.展开更多
The development of non‐precious metal catalysts that facilitate the oxygen evolution reaction(OER)is important for the widespread application of hydrogen production by water splitting.Various perovskite oxides have b...The development of non‐precious metal catalysts that facilitate the oxygen evolution reaction(OER)is important for the widespread application of hydrogen production by water splitting.Various perovskite oxides have been employed as active OER catalysts,however,the underlying mechanism that occurs at the catalyst‐electrolyte interface is still not well understood,prohibiting the design and preparation of advanced OER catalysts.Here,we report a systematic investigation into the effect of proton dynamics on the catalyst‐electrolyte interfaces of four perovskite catalysts:La_(0.5)Sr_(0.5)CoO_(3‐δ)(LSCO),LaCoO_(3),LaFeO_(3),and LaNiO_(3).The pH‐dependent OER activities,H/D kinetic isotope effect,and surface functionalization with phosphate anion groups were investigated to elucidate the role of proton dynamics in the rate‐limiting steps of the OER.For oxides with small charge‐transfer energies,such as LSCO and LaNiO_(3),non‐concerted proton‐coupled electron transfer steps are involved in the OER,and the activity is strongly controlled by the proton dynamics on the catalyst surface.The results demonstrate the important role of interfacial proton transfer in the OER mechanism,and suggest that proton dynamics at the interface should carefully be considered in the design of future high‐performance catalysts.展开更多
The pulsed electron beam rf ion storage system is used to study neon ions electron transfer, The rate coefficients for electron transfer of the neon ions with the neon gas are measured, the results are better than tho...The pulsed electron beam rf ion storage system is used to study neon ions electron transfer, The rate coefficients for electron transfer of the neon ions with the neon gas are measured, the results are better than those in other ion storage system.展开更多
Photo-induced proton coupled electron transfer(PCET)is essential in the biological,photosynthesis,catalysis and solar energy conversion processes.Recently,p-nitrophenylphenol(HO-Bp-NO2)has been used as a model compoun...Photo-induced proton coupled electron transfer(PCET)is essential in the biological,photosynthesis,catalysis and solar energy conversion processes.Recently,p-nitrophenylphenol(HO-Bp-NO2)has been used as a model compound to study the photo-induced PCET mechanism by using ultrafast spectroscopy.In transient absorption spectra both singlet and triplet states were observed to exhibit PCET behavior upon laser excitation of HO-Bp-NO2.When we focused on the PCET in the triplet state,a new sharp band attracted us.This band was recorded upon excitation of HO-Bp-NO2 in aprotic polar solvents,and has not been observed for p-nitrobiphenyl which is without hydroxyl substitution.In order to find out what the new band represents,acidic solutions were used as an additional proton donor considering the acidity of HO-Bp-NO2.With the help of results in strong(~10^-1 mol/L)and weak(~10^-4 mol/L)acidic solutions,the new band is identified as open shell singlet O-Bp-NO2H,which is generated through protonation of nitro O in 3HO-Bp-NO2 followed by deprotonation of hydroxyl.Kinetics analysis indicates that the formation of radical·OBp-NO2 competes with O-Bp-NO2H in the way of concerted electron-proton transfer and/or proton followed electron transfers and is responsible for the low yield of O-Bp-NO2H.The results in the present work will make it clear how the3HO-Bp-NO2 deactivates in aprotic polar solvents and provide a solid benchmark for the deeply studying the PCET mechanism in triplets of analogous aromatic nitro compounds.展开更多
Darboux transformation (DT) provides us with a comprehensive approach to construct the exact and explicit solutions to the negative extended KdV (eKdV) equation, by which some new solutions such as singular solito...Darboux transformation (DT) provides us with a comprehensive approach to construct the exact and explicit solutions to the negative extended KdV (eKdV) equation, by which some new solutions such as singular soliton, negaton, and positon solutions are computed for the eKdV equation. We rediscover the soliton solution with finiteamplitude in [A.V. Slyunyaev and E.N. Pelinovskii, J. Exp. Theor. Phys. 89 (1999) 173] and discuss the difference between this soliton and the singular soliton. We clarify the relationship between the exact solutions of the eKdV equation and the spectral parameter. Moreover, the interactions of singular two solitons, positon and negaton, positon and soliton, and two positons are studied in detail.展开更多
文摘The mechanism of the proton_transfer_coupled electron transfer (PT_ET) reactions between the menaquinone Q A (MQ 1) and ubiquinone Q B (UQ 1) in the bacterial photosynthetic reaction center of Rhodopseudomona viridis was studied by using the B3LYP/6_31G(d) method. The changes of standard Gibbs free energy ΔG 0 of all possible reactions followed the ET reaction (1) were calculated. The results indicated that: (1) according to the ΔG 0 values of corresponding reactions, UQ 1 could not accept two electrons from MQ - 1 continually without the coupled proton transfer reactions. Because of ΔG 0 2b 0, ΔG 0 3b 0 and ΔG 0 4b 0, the corresponding PT_ET reactions could take place along with reactions (2b), (3b) and (4b) sequentially; (2) on the gaseous condition, the first and second transferred protons (H +(1) and H +(2)) from the surrounding amino acid residues or water molecules will combine with the oxygen No.7 and oxygen No.8 of UQ 1, respectively. On the condition of protein surroundings (by SCRF model, ε =4.0), the results are converse but the energy difference between the combination of H +(1) and H +(2) with UQ - 1 is quite small. The difference of ΔG 0 values between the corresponding reactions in gaseous surroundings and the SCRF model is not significant; (3) the PT_ET reactions between MQ 1 - and UQ 1 - should be as follows: MQ 1 -+UQ 1→MQ 1+UQ 1 - (1) UQ 1 - ( O (7) )+H +( HisL 190)→UQ 1H(2b) ( Gas ) or UQ 1 - ( O (8) )+H +(H 2O)→UQ 1H (2b') ( SCRF ) or UQ 1 - ( O (8) )+H + ( ArgL 217)→UQ 1H(2b') ( SCRF ) MQ 1 -+UQ 1H→MQ 1+UQ 1H - (3b) ( Gas ) MQ 1 -+UQ 1H→MQ 1+UQ 1H -(3b') ( SCR F) UQ 1H -+H +(H 2O)→UQ 1H 2(4b) ( Gas ) or UQ 1H -+H + ( ArgL 217)→UQ 1H 2 (4b) ( Gas ) or UQ 1H -+H + ( HisL 190)→UQ 1H 2 (4b') ( SCRF )
基金This work was supported by project "Regulation of Composition and Saturation of Fatty Acid in Trees by Genetic Engineering", Introduction of Foreign Advanced Agricultural Science and Technology into China (No. 2005-4-52).
文摘Acyl-ACP thioesterases (FATs) terminates the fatty acid synthesis and allow the transport of fatty acids out of the plastids, which are the important determinants of cellular metabolism. FATB is a member of FAT enzymes that has been described previously in most of the plants. In silico cloning is a new method that utilizes the bioinformatics on the complete genome and available EST database. In this study, a full-length cDNA clone of PtFATB gene was isolated from Populus tomentosa using this approach. It is 1,450 bp in length and the open reading frame encodes a peptide of 421 amino acids. The predicted amino acid sequence shows significant homology with those from other plant species, which contain typical domains owned by FATB proteins. The transcripts of PtFATB were abundant in leaves, and less in roots detected by using semiquantitative RT-PCR. When the shoots were subjected to the stress treatments (cold, dry, NaC1) and ABA (Abscisic acid), the expression of PtFATB was only slightly reduced under the treatment of low temperature. This suggests that the expression of PtFATB is in a constitutive fashion. This study provides the basis not only for the identification and characterization of this gene but also for the improvement of cold tolerance by controlling the expression of the PtFATB gene in trees in near future.
文摘The reverse snapback phenomena (RSP) on I-V characteristics of static induction thyristors (SITH) are physically researched. The I-V curves of the power SITH exhibit reverse snapback phenomena, and even turn to the conducting-state,when the anode voltage in the forward blocking-state is increased to a critical value. The RSP I-V characteristics of the power SITH are analyzed in terms of operating mechanism, double carrier injection effect, space charge effect, electron-hole plasma in the channel, and the variation in carrier lifetime. The reverse snapback mechanism is theoretically pro- posed and the mathematical expressions to calculate the voltage and current values at the snapback point are presented. The computing results are compared with the experiment values.
文摘A series of donor-π-acceptor (D-π-A) compounds involving varied donors and acceptors as well as a dihydroquinolinone moiety were synthesized. Tuned fluorescent colors from blue to orange were successfully realized in them. Spectroscopic analysis exhibits that the increased conjugated system, enhanced electrondonating ability of acceptor, and electron-withdrawing ability of donor result in red shift in both absorption and fluorescence for these compounds. Both the absorption and fluorescence show strong bathochromic shift effect with the increase in the polarity of solvents. It indicates that they are intramolecular charge transfer (ICT) fluorescent compounds and may have potential application as novel electroluminescent material.
基金This work was supported by the Natural Science Foundation of Universities of Inner Mongolia Autonomous Region (No.NG09168 and NG10239).
文摘A new anion receptor bearing phenolic hydroxy group based on 3,5- ditertbutylsalicylaldehyde-p-nitrophenylhydrazone (1) was designed and synthesized. Upon addition of AcO- and F-, the receptor exhibited visible color changes from deep yellow to purple. However, no obvious color changes were observed on addition of the other anions tested (H2PO4-, Cl-, Br-, I-). The binding properties of the receptor with anions such as AcO and F- were investigated by UV-Vis and fluorescent titrations. The result indicated that the receptor 1 had a higher affinity to AcO- and F- and a 1:1 host-guest complex was formed through H-bond interactions between 1 and anions.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (No.61137005 and No.10974023), the Program for Liaoning Excellent Talents in University (No.LJQ2012002), and the Program for New Century Excellent Talents in University (No.NCET-12-0077).
文摘The excited state intramolecular proton transfer (ESIPT) coupled charge transfer of baicalein has been investigated using steady-state spectroscopic experiment and quantum chemistry calculations. The absence of the absorption peak from S1 excited state both in the experi-mental and calculated absorption spectra indicates that S1 is a dark state. The dark excited state S1 results in the very weak fluorescence of solid baicalein in the experiment. The fron- tier molecular orbital and the charge difference densities of baicalein show clearly that the S1 state is a charge-transfer state whereas the S2 state is a locally excited state. The only one stationary point on the potential energy profile of excited state suggests that the ESIPT reaction of baicalein is a barrierless process.
基金supported by the National Natural Science Foundation of China(No.21806018 and No.21873052)the Fundamental Research Funds for the Central Universities(DUT20RC(4)002)+1 种基金Scientific Research Grant of Ningbo University(No.215-432000282)Ningbo Top Talent Project(No.215-432094250)。
文摘The divergent behavior of C-H bond oxidations of aliphatic substrates compared to those of aromatic substrates shown in Gupta’s experiment was mechanistically studied herein by means of density functional theory calculations.Our calculations reveal that such difference is caused by different reaction mechanisms between two kinds of substrates(the aliphatic cyclohexane,2,3-dimethylbutane and the aromatic toluene,ethylbenzene and cumene).For the aliphatic substrates,C-H oxidation by the oxidant Fe^(V)(O)(TAML)is a hydrogen atom transfer process;whereas for the aromatic substrates,C-H oxidation is a proton-coupled electron transfer(PCET)process with a proton transfer character on the transition state,that is,a proton-coupled electron transfer process holding a proton transfer-like transition state(PCET(PT)).This difference is caused by the strongπ-πinteractions between the tetra-anionic TAML ring and the phenyl ring of the aromatic substrates,which has a“pull”effect to make the electron transfer from substrates to the Fe=O moiety inefficient.
文摘Deuterium labeling techniques are widely utilized as efficient tools to study the absorption,distribution,metabolism,and excretion(ADME)of pharmaceuticals.Moreover,deuterium‐labeled drugs are expected to prolong the half‐life of drug metabolism,enhance the efficacy of drugs,close metabolic sites,and decrease side effects.Thus,there is a rising demand for the practical construction of deuterium‐labeled drugs and their intermediates under mild conditions.This paper timely provides an overview of the recent advances in both photo‐and electro‐catalytic mild and selective deuteration of fine chemicals and pharmaceuticals with low‐cost and sustainable deuterium source.Three types of deuteration strategies are discussed according to the deuteration mode,named deuterium atom transfer strategy,deuterium atom abstraction strategy and deuterated water splitting strategy respectively.The application scope and mechanistic insights are discussed comprehensively.Finally,the perspective on the challenges and future development trends for photo‐and electro‐catalytic deuteration strategies are also presented.
基金supported by the National Key R&D Program of China(No.2018YFA0209100 and No.2017YFA0303703)the National Natural Science Foundation of China(No.21922302,No.21873047,No.91850105,and No.91833305)+1 种基金the Fundamental Research Funds for the Central Universities(No.020414380126)Chun-feng Zhang acknowledges financial support from the Tang Scholar Program。
文摘Cyano substitution has been established as a viable approach to optimize the performance of all-small-molecule organic solar cells.However,the effect of cyano substitution on the dynamics of photo-charge generation remains largely unexplored.Here,we report an ultrafast spectroscopic study showing that electron transfer is markedly promoted by enhanced intermolecular charge-transfer interaction in all-small-molecule blends with cyanided donors.The delocalized excitations,arising from intermolecular interaction in the moiety of cyano-substituted donor,undergo ultrafast electron transfer with a lifetime of∼3 ps in the blend.In contrast,some locally excited states,surviving in the film of donor without cyano substitution,are not actively involved in the charge separation.These findings well explain the performance improvement of devices with cyanided donors,suggesting that manipulating intermolecular interaction is an efficient strategy for device optimization.
基金Project supported by the Scientific Research Foundation for theReturned Overseas Chinese Scholars, State Education Ministry andZhejiang Provincial National Science Foundation of China
文摘A new configuration integrated ion exchange effect with both electro-migration and electrochemical reaction in a single cell was developed to effectively retrieve metal ions from simulated wastewater using ion exchange resins without additive chemicals. By simply assembling cation exchange resins and anion exchange resins separated by homogeneous membranes, we found that the system will always be acidic in the concentrate compartment so that ion exchange resins could be in-situ regenerated without hydroxide precipitation. Such a realizable design will be really suitable for wastewater purification.
基金supported by the Science Challenge Project(No.TZ2016001)the National Natural Science Foundation of China(No.21673211)
文摘Photo-induced electron transfer versus molecular structure of acceptors is investigated using ultrafast time-resolved transient grating spectroscopy. Typical laser dyes Rhodamine 101 (Rh101) and Rhodamine 6G (Rh6G) in electron donor solvent-aniline are adopted as the objects. The forward electron transfer time constant from aniline to the excited singlet state of two Rhodamine dyes and subsequent back electron transfer from two dyes to aniline are measured. The experimental results denote that Rh6G presents faster electron transfer rates with aniline in both forward electron transfer and back electron transfer processes. With chemical calculation and qualitative analysis, it is found that the flexible molecular geometry of Rh6G leads to stronger electron coupling with donor solvent and further gives rise to larger electron transfer rates.
文摘The development of non‐precious metal catalysts that facilitate the oxygen evolution reaction(OER)is important for the widespread application of hydrogen production by water splitting.Various perovskite oxides have been employed as active OER catalysts,however,the underlying mechanism that occurs at the catalyst‐electrolyte interface is still not well understood,prohibiting the design and preparation of advanced OER catalysts.Here,we report a systematic investigation into the effect of proton dynamics on the catalyst‐electrolyte interfaces of four perovskite catalysts:La_(0.5)Sr_(0.5)CoO_(3‐δ)(LSCO),LaCoO_(3),LaFeO_(3),and LaNiO_(3).The pH‐dependent OER activities,H/D kinetic isotope effect,and surface functionalization with phosphate anion groups were investigated to elucidate the role of proton dynamics in the rate‐limiting steps of the OER.For oxides with small charge‐transfer energies,such as LSCO and LaNiO_(3),non‐concerted proton‐coupled electron transfer steps are involved in the OER,and the activity is strongly controlled by the proton dynamics on the catalyst surface.The results demonstrate the important role of interfacial proton transfer in the OER mechanism,and suggest that proton dynamics at the interface should carefully be considered in the design of future high‐performance catalysts.
文摘The pulsed electron beam rf ion storage system is used to study neon ions electron transfer, The rate coefficients for electron transfer of the neon ions with the neon gas are measured, the results are better than those in other ion storage system.
基金supported by the National Natural Science Foundation of China(No.21973082)。
文摘Photo-induced proton coupled electron transfer(PCET)is essential in the biological,photosynthesis,catalysis and solar energy conversion processes.Recently,p-nitrophenylphenol(HO-Bp-NO2)has been used as a model compound to study the photo-induced PCET mechanism by using ultrafast spectroscopy.In transient absorption spectra both singlet and triplet states were observed to exhibit PCET behavior upon laser excitation of HO-Bp-NO2.When we focused on the PCET in the triplet state,a new sharp band attracted us.This band was recorded upon excitation of HO-Bp-NO2 in aprotic polar solvents,and has not been observed for p-nitrobiphenyl which is without hydroxyl substitution.In order to find out what the new band represents,acidic solutions were used as an additional proton donor considering the acidity of HO-Bp-NO2.With the help of results in strong(~10^-1 mol/L)and weak(~10^-4 mol/L)acidic solutions,the new band is identified as open shell singlet O-Bp-NO2H,which is generated through protonation of nitro O in 3HO-Bp-NO2 followed by deprotonation of hydroxyl.Kinetics analysis indicates that the formation of radical·OBp-NO2 competes with O-Bp-NO2H in the way of concerted electron-proton transfer and/or proton followed electron transfers and is responsible for the low yield of O-Bp-NO2H.The results in the present work will make it clear how the3HO-Bp-NO2 deactivates in aprotic polar solvents and provide a solid benchmark for the deeply studying the PCET mechanism in triplets of analogous aromatic nitro compounds.
基金supported by National Natural Science Foundation of China under Grant No.10601028
文摘Darboux transformation (DT) provides us with a comprehensive approach to construct the exact and explicit solutions to the negative extended KdV (eKdV) equation, by which some new solutions such as singular soliton, negaton, and positon solutions are computed for the eKdV equation. We rediscover the soliton solution with finiteamplitude in [A.V. Slyunyaev and E.N. Pelinovskii, J. Exp. Theor. Phys. 89 (1999) 173] and discuss the difference between this soliton and the singular soliton. We clarify the relationship between the exact solutions of the eKdV equation and the spectral parameter. Moreover, the interactions of singular two solitons, positon and negaton, positon and soliton, and two positons are studied in detail.